AU625333B2

AU625333B2 - Method of analysing a liquid

Info

Publication number: AU625333B2
Application number: AU18852/88A
Authority: AU
Inventors: Norman Mcmillan
Original assignee: Frayne John
Current assignee: Frayne John
Priority date: 1987-04-10
Filing date: 1988-07-08
Publication date: 1992-07-09
Anticipated expiration: 2008-07-08
Also published as: AU1885288A; EP0286419A3; EP0286419A2; DE3872427T2; ATE77881T1; JPS6438633A; DE3872427D1; ZA882454B; US4910402A; EP0286419B1

Abstract

An apparatus for measuring a property of a liquid comprises at least one guide (10) for electromagnetic radiation, means (20) for directing electromagnetic radiation into the guide, means (16) for providing at least one drop of liquid (15) in contact with the guide at a position where radiation from the guide can enter the drop, and means (22) for deriving a signal which is a function of the interaction of the radiation with the liquid of the drop.

Description

COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 Form COMPLETE SPECIFICATION FOR OFFICE USE Short Title: Int. Cl Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed; Published: Priority: Related Art: TO BE COMPLETED BY APPLICANT Name of Applicant: Address of Applicant: Actual Invontor: Address for Service: NORMAN McMILLAN Whitebutts, Killeshin Road, Craiguecullen, Carlow, County Carlow, REPUBLIC OF

IRELAND

Norman McMillan GRIFFITH HACK CO.

71 YORK STREET SYDNEY NSW 2000

AUSTRALIA

Complete Specification for the invention entitled: METHOD OF ANALYSING A LIQUID The following statement Is a full description of this invention, including the best method of perforning it known to me/us:- 6504A:rk I, -2- The invention relates to an apparatus and method for measuring a property of a liquid.

According to the invention there is provided an apparatus for measuring a property of a liquid, comprising at least one electromagnetic radiation guide having a downwardly-facing free end, first means for directing electromagnetic radiation into the guide for guidance to the free end thereof, second means for forming at least one drop of liquid at the free end of oo the guide by supplying liquid to, flow under gravity down 04 o4 a surface to the said free end of the guide, and third 0 4 means for deriving a signal which is a function of the interaction of the radiation with the liquid of the drop by detecting the amplitude of the radiation reflected internally of the drop into the same or a second guide.

tl The liquid may be formed as a static drop suspended i at the free end of the radiation guide, e.g. a light guide, or it may be a dynamic drop one of a succession of drops allowed to drip from the end of the guide.

Thus one can perform measurements on small volumes, or continuously monitor a liquid in a flow process by bleeding off sample droplets for measurement.

The electromagnet radiation may be any such radiation which can be guided along a radiation guide to the drop, and may be continuous, pulsed or otherwise modulated to facilitate the particular analysis being performed.

:-w 3 The electromagnetic radiation supplied to the drop along the guide may be combined with other electromagnetic energy or other forms of energy (for example acoustic energy) also supplied to the drop, either applied along the guide, by an external field or by any other method of energising the drop. Such other forms of energy may be used to pump a process in or outside th drop in order to change the conditions relating to the measurement being performed.

The temperature or other ambient conditions may be changed in any desired manner to vary the physical conditions for the measurement or as experimental control variables.

The signal which is a function of the interaction of the liquid with the radiation may be derived by any device appropriate to the particular analysis, and may comprise a dedicated instrument or system or an instrument or system with general applications.

Most simply, the signal is derived by measuring the level of radiation reflected internally of the drop into the same or a further radiation guide. However, other forms of sensor or probe may be used.

The invention further provides a method for measuring a property of a liquid, comprising at least one electromagnetic radiation guide having a downwardly-facing free end, first means for directing electromagnetic radiation into the guide for guidance to the free end thereof, second means for forming at least one drop of liquid at the free end of the guide by supplying liquid to flow under gravity down a surface to the said free end of the guide, and third means for -4deriving a signal which is a function of the interaction of the radiation with the liquid of the drop by detecting the amplitude of the radiation reflected internally of the drop into the same or a second guide.

Although the invention is described herein using optical fibres as radiation guides, the latter could be formed by other radiation-guiding means such as capilliary tubes or other radiation guides.

Furthermore, while the invention is described herein in terms of supplying the drop to the radiation guide by gravity feed, other technique& are possible.

For example, drop could be formed and suspended in an electric field, and brought to the measuring position from below, or from the side. This would also permit making some measurements while the drop is approaching the guide.

Also, the drop need not be attached to the end of the guide, as described herein. It can be attached to any part of the guide where the radiation is capable of passing into it, for example, at an intermediate position on the guide where the radiation is coupled into the drop via the evanescent wave.

The invention can be used inter alia to measure a wide range of physical, chemical, electrical, opto-acoustical and other properties of the liquid, either singly or in any combination. These include: i. Refractive index.

2. Surface tension.

S- 5 3. Specific gravity.

4. Viscosity (absolute or kinematic).

Turbidity.

6. Absorption or chemical composition.

7. Fluorescence.

8. pH.

00 0 o 0 0 0, o9. Conductivity or ion type.

0 0 tt Opto-acoustical properties.

11. Adhesion or other mechanical properties.

12. Pressure head.

13. Liquid volume.

14. Any other properties, such as humidity, which may condition the drop and so be indirectly measured.

Embodiments of the invention will now be described, by way of example, with reference to the accompanying drawings, in which: Figure 1 is a schematic diagram of an embodiment of an apparatus for performing the invention; Figure 2 is an enlarged view of the downwardly facing free ends of the optical fibres shown in Figure 1; 99 9 9 99 9 99 10 99 99~ 0 9 99 99 9 9 99 99 99 9 9 99 9 990099 9 9 9 99 99 9 9 9 ~9 94 9 099 15 99 4 999 6 6- Figure 3 illustrates how the fibres may be securely supported in the position shown in Figure 2 for handling and protection; Figure 4 is a voltage/time diagram of a typical signal produced by the detector circuit of Figure 1 for a transparent liquid with low absorption; Figure 5 is a similar voltage/time diagram for a liquid having significant absorption; Figure 6 shows a form of the apparatus for measuring pH; Figure 7 shows a form of the apparatus for measuring conductivity; and Figures 8 to 10 illustrate alternative light guide and detection arrangements.

Referring to Figure 1, first and second radiation guides in the form of optical fibres 10 and 11 are brought close together at their downwardly facing free ends 12 and 13 respectively. The free end of a liquid feed pipe 14 is also brought into close proximity to the ends 12 and 13 of the optical fibres, so that liquid supplied by the latter can form a drop 15, or a succession of drops, at the ends of the fibres.

The pipe 14 may be supplied by a syringe type plunger so that a single static drop 15 may be formed, or alternatively the pipe 14 may be fed by a constant head of liquid from a constant head apparatus so that a succession of reprodlwible drops 1.5 are fed under gravity to the onds 12 and 1.3 of the optical fibres and -t7 allowed to drip therefrom. These alternatives are schematically shown at 16, and are so well known that no detailed description is thought necessary.

Referring to Figure 2, which shows the free ends of the fibes 10 and 11 and the pipe 14 to an enlarged scale, at their free ends 12 and 13 the axes of the fibres 10 and 11 are disposed symmetrically on either side of a vertical plane 17 at an angle of 18 0 to 220 with respect to one another, and preferably at an angle of 200 as shown.

The fibres may be polymethyl methacrylate fibres with an actual fibre core diameter (i excluding the outer casing) of 1mm. The centres of their lower ends are spaced apart by about 2.6 mm as shown. The fibres may be step index fibres. Graded index or inonomode fibres may be used although it will be readily understood that in such cases other geometries must be used for optimum working. It will be noted that the I I pipe 14 is offset fromi the centre plane 17 between the fibres 10 and 11, so that the liquid flows down the f ibre 11 to the ends 12 and 13.

In order to securely support the fibres 10 and 11 and the pipe 14 in their relative positions shown in Figure 2, their lower free ends are fixed in epoxy resin 18 in a glass cylinder 19, Figure 3, the lower end of the cylinder extending slightly below the free ends 12 and 13 of the fibres for protection and handling.

Referring again to Figure 1, infra-red (IR) or visibl~e radiation in the range 0.3um to l.3um is supplied by an LED, solid state laser or other I I T I I 8radiation source 20 which directs radiation into the end of the optical fibre 10 remote from the drop and such radiation travels along the fibre 10 to the drop The radiation may be continuous, varied in a cyclic manner, or otherwise varied to facilitate a particular measurement. In the present case the radiation source 20 is a "Honeywell Sweet Spot" pulsed LED operated in the range 50Hz to 10KHz by a square wave signal generator 21. The generator 21 provides 00 for stable operation of the LED 20, as well as 0 providing advantages in measurement to be describ-a.

0.0 0 o Radation from the source 20 travels along the o° fibre 10 to reach the drop 15 and is reflected 15 internally of the drop 15 to travel up to the second optical fibre 11 to a detector circuit 22 an IR detector or light-dependent resistor) where the level of the reflected radiation is measured. For example, 0:0 the detector 22 may be an infra-red phototransistor 20 configured in a simple potential divider circuit with 00 approximately 9 volts supply. The detected output level is supplied to one or more of a digital voltmeter 23, a storage oscilloscope 24, a chart recorder 25 and 0l a data logging computer 26 with associated printer 27.

In the case of a liquid drop held suspended at the ends 12 and 13 of the optical fibres, i.e. a static drop, the level of radiation reflected up on the optical fibre 11, as measured by the digital voltmeter 23, is directly proportional so the refractive index of the liquid, assuming constant drop size and absorbance.

a -9- It was found in the static mode by experiment that the most reproducible results were obtained by careful tilting of the apparatus out of the vertical plane out of the plane of Figure 2) and adjusting the drop size, using the syringe, to obtain a maximum signal. It will be noted that the modulation of the IR source 20 by the generator 21 is not registered by the digital voltmeter 23.

Thus, by taking voltmeter reading for liquids of known refractive index and plotting these as a straight line graph of refractive index against the voltmeter reading, the refractive index of any other liquid can be determined from the graph by its voltmeter reading.

Other properties of the liquid can also be determined by the static method, for example, absorbance (concentration of dissolved chemicals in a given solvent).

Conventionally, absorbance is measured using a cuvette. Light is passed through the cuvette, and the absorbance A is given by A log(Io 0 where 10 is the incident intensity and I is the intensity after passing through the cuvette. Since A E.c.l where E extinction coefficient, p concentration and 1 distance travelled by the light through the cuvette, g (concentration) can be determined from A, since E can be obtained from reference books and i1 is known for the cuvette.

However, cuvettes are subject to variations in tolerance, and since a drop 15 can be reproduced almost exactly on the present apparatus, it can therefore effectively constitute an almost ideal cuvette. Thus by plotting A against c for liquids of known concentration, where in this case Io input level to the drop and I output level as measured by the digital voltmeter 23, a calibration curve can be obtained.

In the case of dynamic drops, Figure 4 showns (for a relatively transparent liquid with low absorption) the voltage/time diagram as each drop falls from the ends of the optical fibres 10 and 11 into the beaker 28. This diagram will be produced by the oscilloscope 24, the chart recorder 25, and the printer 27 of the computer 26. The broad peak 30 corresponds to the growth of the drop, and the final narrow peak 31 is from the ends of the optical fibres.

It is to be understood that the diagram used in the present analysis is one where the height of the narrow peak 31 is as close to the height of the broad i peak 30 as possible, and this is achieved by tilting the apparatus as previously described until the best results are achieved.

From such a diagram, the time period T 2 can be used to determine the refractive index of the liquid using a calibration procedure. Thus, if n (refractive index) is plotted against T 2 /V (where V volume per second) for a number of liquids of known refractive index, a calibration curve is obtained which can be used to determine the refractive index of liquids whose refractive index is not known.

Further, the overall cycle period T 1 of the diagram is a function of the surface tension of the liquid and the kinematic viscosity in a gravity feed constant head apparatus. The kinematic viscnsity can be determined by a calibration technique from the slope 32, and the surface tension can then be determined from the kinematic viscosity and T.

The width of the peak 31 at half its amplitude is a measure of the specific gravity of the liquid.

other properties can be determined by processing the data from the trace, either manually from the trace or by suitably programming the computer 26. In this connection, the square wave superimposed on the trace assists in ascertaining the various measuring points required. Differentiation and double differentiation will also help to identify points of interest, and if necessary, any modulation applied by the generator 21 (Figure 1) can be filtered out before this is done.

Figure 5 shows how the trace of Figure 4 is modified by absorption. For chemical analysis, an analysis time T A is fixed and the height of the signal S Ifor an absorbing liquid can be measured for different concentrations at one measurement wavelength, A graph of absorbance A =log(S 0 /Sj) can be plotted against concentration and from this calibration graph the concentration of an unknown solution can be determined.

Alternatively, chemical analysis may be performed by integrating the detected signal, i.e. measuring the area under the trace during the cycle period TV. The area will decrease with increasing concentration.

The analysis off turbidity can be done in a similar fashion by measuring the decrease in S 0 with increasingly turbid solutions.

-1 12 If the liquid is flourescent, then an excitation wavelength, such as UV or blue, can be used and the signal measured at the detector 22 which in this case has a monochromatic filter at a longer wavelength, such as orange, placed in front of it. The measurement would be done by the standard fluorescent methods of plotting this signal against the concentration of the fluorescent substance to obtain a calibration graph from which an unknown can be determined.

Referring now to Figure 6, the appartus is shown modified to measure pH. In this case, a pair of large area capacitor plates 40 and 41 are disposed respectively one above and one below the free ends 12 and 13 of the optical fibres, and are separated from the latter by 4 to 5 cm.

Each drop 15 becomes charged as it detaches from the ends of the fibres, usually positively under normal atmospheric conditions, which charges up the lower plate 41 of the capacitor. Thus the drops are increasingly repelled, so that T increases until a 1 mauintu is reached where the additional charge from each drop equals the leakage from the plate 41. This maximum value of T 1 gives a measure of the pH value of the liquid.

An AC or DC voltage supply can be connected across the plates of the capacitor to vary TI, and these variations can be related to the electrical properties of the liquid. Likewise, the liquid feed could be charged to vary T i The pH of the solution can be obtained by placing i -a~ 13 the drop in an electric field and the drop time, T 1 can be made to vary according to the 1 developed on the capacitor.

A voltage will appear by self charging of the capacitor due to the rupture of the drop from the body of supporting liquid, and this will lead to an increase o in the drop time, which itself will be a function of the electrical properties of the liquid. The electrical condition of the atmosphere can be monitored 1O 0 via the simple fibre drop analyser by connecting the liquid drop feed to a boltmeter and allowing the induced change on the drop to continue to carry away change until the equilibrium situation is obtained when the voltage of the feed equates with the voltage of the o 15 potential of the surrounding air.

Referring to Figure 7, the conductivity of a a oliquid can be measured by providing respective electrodes 42 and 43 adjacent the free ends of each fibre 10 and 11 respectively. Respective conductors 44 and 45 extending from each electrode along the exterior of each fibre in the direction away from the free ends permit connection of the electrodes 42 and 43 to an external electrical circuit comprising, in this case, a constant voltage supply 46 and an ammeter 47.

An alternative bubble analysis can be devised to work on the principle above, with downward facing and inwardly pointing fibres directed at a liquid surface to carry out the analysis on an exploding bubble released from the bottom of a container.

The foregoing describes just some of the many uses of the apparatus described.

14 For example, the apparatus can be used as a rain guage. If the syringe or constant head apparatus 16 is replaced by, for example, a funnel open at the top to rainfall and whose bottom is connected to the pipe 14, the rainfall may be measured by counting the total number and/or frequency of drops. This measurement may be effected, for example, by counting the broad peaks of the trade in the computer 26 or in a separate counter.

Also, the time T 1 could be used to monitor pressure head where this was important for control purposes.

The dynamic properties of a liquid may be examined with the drop in situ. Thus the drop can be caused to oscillate, while remaining on the ends of the fibres, by the application of varying electromagnetic or electrostatic fields, or by mechanical vibration. In this case the trace would have symmetrical peaks and no peaks 31. The period, amplitude and phase of the oscillations, as measured by the detector 22, would give information regarding the mechanical and/or electrical properties of the liquid depending on the circumstances of the procedure.

While the above has shown an arrangement where there are two optical fibres, a source fibre and a receiving fibre, other geometries for the fibre optics or other light guides are possible.

Thus, as shown in Figure 8, the source fibre injects light into a drop which couple, into two receiving optical fibres 11' and 11" which can detect individually the quantity of radiation coupled to a 15 respective detector at the end of the fibre, or it may be used to compare the difference between the light coupled to produce a differential analyser.

In Figure 9, a single bifurcated optical fibre is used, the left hand branch 10 constituting the source, and the right hand branch 11 the receiver. This design o :produces an increased coupling to the receiving fibre when the fibre is tilted, but one which is asymmetric having a preferential clockwise tilt. A multi-fibre 1o 0 system could also be used to carry many wavelengths oo into the drop to enable, for example, the chemical l analysis of several components simultaneously.

o 4 Finally, in Figure 10, a single fibre 10 may be 4 94o used, and detection is accomplished by a sensitive S. 15 opto-acoustical microphone 50 and amplifier 51 which detects the sound produced in the sample by the pulsed source (17, 18 in Figure In this case the sample liquid may be opaque and does not need to transmit radiation.

The contmercial applications of the apparatus are many: 1. A system monitor and controller for an industrial flow process.

2. A water monitor for monitoring a selection of quantities for a reservoir or industrial process.

3. A household water quantity and quality meter.

4. A rain guage to measure the properties of rain water, e.g. acid rain.

U sm l 1 il. 1111 S- 16- A laboratory liquid analyser, either dedicated for a specific application or general purpose.

6. A medical or clinical drip analyser.

7. A saccharimeter.

Naturally the use of an opto-acoustical microphone is not limited to the embodiment of Figure 10 but could be used more generally, for example, in relation to the receiving fibre 11 in Figure 1.

Claims

1. An apparatus for measuring a property of a liquid, comprising at least one electromagnetic radiation guide having a downwardly-facing free end, first means for directing electromagnetic radiation into the guide for guidance to the free end thereof, second means for A I ~c~r yFror-\ forming at least one drop of liquid Ar\tne free end of the guide by supplying liquid to flow under gravity down a surface to the said free end of the guide, and third means for deriving a signal which is a function of the interaction of the radiation with the liquid of the drop by detecting the amplitude of the radiation reflected internally of the drop into the same or a second guide.

2. An apparatus according to Claim i, comprising a first and second electromagnetic radiation guides having respective downwardly-facing free ends closely adjacent to one another with the guides diverging upwards away from the free ends, wherein the first means directs electromagnetic radiation into the first guide for guidance towards the free end thereof, the second means forms at least one drop of liquid suspended in common from the free ends of both the first and second guides, and the third means for derives a signal which is a function of the interaction of the radiation with the liquid of the drop by detecting the amplitude of the radiation reflected internally of the drop into the 4 second guide.

3. An apparatus according to Claim 2, wherein at their free ends the axes of the first and second radiation guides are disposed at an angle of between 180 and 220 with respect to one another. -C 18

4. An apparatus according to Claim 1, wherein the first means comprises a light emitting diode.

An apparatus according to Claim 1, wherein the first means comprises a laser.

6. An apparatus according to Claim 1, wherein the radiation is modulated before entering the drop.

7. An apparatus according to Claim 1, wherein the radiation is infra red or visible light in the range 0.3 uim to 1.3 umn. g: 10

8. An apparatus according to Claim 1, wherein the second means comprises means for providing a succession of drops which drip from the free end of the guide.

9. An apparatus according to Claim 8, wherein the second comprises a constant head apparatus.

10. An apparatus according to Claim 1, wherein the second means comprises means for providing a single static drop at the free end of the guide.

11. An apparatus according to Claim 1, wherein the said at least one guide is an optical fibre.

12. A method for measuring a property of a liquid, comprising providing at least one electromagnetic radiation guide having a downwardly-facing free end, directing electromagnetic radiation into the guide for guidance to the free end thereof, forming at least one\ drop of *e liquid a*the free end of the guide by supplying liquid to flow under gravity down a surface to the said free end of the guide, and deriving a signal n j- 19 which is a function of the interaction of the radiation with the liquid of the drop by detecting the amplitude of the radiation reflected internally of the drop into the same or a second guide.

13. An apparatus for measuring a property of a liquid substantially as herein described with reference to Figs. 1 to 5, Fig. 6, Fig. 7 and Figs. 8 to 10 of the accompanying drawings. DATED this 14th day of March 1991 NORMAN McMILLAN By his Patent Attorneys GRIFFITH HACK CO.